Silver halide color photographic light-sensitive material

ABSTRACT

A COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL COMPRISING A SUPPORT HAVING COATED THEREON A RED-SENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING A CYAN-COLOR FORMING COUPLER, A GREEN-SENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING A MAGENTA-COLOR FORMING COUPLER, AND A BLUE-SENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING A YELLOW FORMING COUPLER AND A COMPOUND REPRESENTED BY THE FORMULA   R-N&lt;(-Z-C(=C&lt;(-Q-C(=O)-))-)   WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A SULFOALKYL GROUP AND A SULFOARALKYL GROUP, AND Z AND Q ARE EACH AN ATOMIC GROUP NECESSARY TO COMPLETE A HETEROCYCLIC NUCLEUS.

June 27, 1972 AKIRA SATO ET AL 3,672,897

SILVER HALIDE COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL Filed Sept. 16, 1969 REL ABS. 1 x

REL. ABS.

REL. ABS.

INVENTORS AKIRA SATO HIROZO UEDA YOSHIAKI ONO BY Ah 2M, M

EM cf Qua/flak ATTORNEYS United States Patent 3,672,897. Patented June 27, 1972 3,672,897 SILVER HALIDE COLOR PHOTOGRAPHIC LIGHT- SENSITIVE MATERIAL Akira Sato, Hirozo Ueda, and Yoshiaki Ono, Kanagawa,

Japan, assignors to Fuji Photo Film Co., Ltd., Kauagawa, Japan Filed Sept. 16, 1969, Ser. No. 858,262 Claims priority, application Japan, Sept. 16, 1968,

3/66,821 Int. Cl. G03c 1/40 US. CI. 96-74 13 Claims ABSTRACT OF THE DISCLOSURE ing coupler and a compound represented by the formula ,-Q-. RN-C= o=o wherein R is a member selected from the group consisting of a sulfoalkyl group and a sulfoaralkyl group, and Z and Q are each an atomic group necessary to complete a heterocyclic nucleus.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to a silver halide color photographic light sensitive material. More particularly, it is concerned with a spectrally sensitized, coupler-containing silver halide color photographic light-sensitive material.

Description of the prior art In general, a silver halide color photographic light-sensitive material, on the basis of subtractive color principles, consists of a support and red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers coated thereon, the emulsion layers each containing one or more coupler compounds capable of reacting with the oxidation product of a paraphenylene-diamine derivative to form a dye image.

It is necessary for desirable color reproducibility of such light-sensitive materials to appropriately select the spectrally sensitive regions of the three silver halide emulsion layers corresponding to the spectral characteristics of the dye image formed by the reaction between the oxidation product of a paraphenylenediamine derivative and a coupler. For instance, with respect to the spectrally sensitive region of a blue-sensitive emulsion layer, the inherently sensitive region of the silver halide is normally utilized as it is, but the spectral absorption of the silver halides lies near the ultraviolet region and is not suitable for the spectral characteristics of a yellow dye image and, accordingly, the disadvantage of a poor yellow reproducibility results. To alleviate this problem, a process has been practiced in which the blue-sensitive emulsion layer is spectrally sensitized to impart thereto an absorption characteristic in a longer wave length region. The following dyestufis are known as spectral sensitizers used to accomplish the above purpose.

=CH-CH S H a 0 CHa CzH5 However, dyestufi 1) is inadequate because the spectrally sensitive region of a blue-sensitive emulsion layer is excessively extended toward the longer wave length side when dyestulf (1) is incorporated therein, and thus, as a result, the sensitized emulsion exhibits a poor reproducibility of green objects when used as a silver halide color photosensitive material in the subtractive color process. In addition, dyestufi (2) decreases the inherent sensitivity of a silver halide in the blue-sensitive emulsion layer when incorporated therein, and affords an undesirable spectral sensitization region to the blue-sensitive emulsion layer.

Moreover, in general, known spectral sensitizers have the drawback that when they are incorporated in a silver halide emulsion layer they often cause an undesirable color stain in the layer after processing and furthermore, as is the case with dyestuff (2), there occurs a desorption of the spectral sensitizer which has been adsorbed by the silver halide either during the multi-layer coating process or during storage under high temperature and high humidity conditions after coating, which results in a decrease of blue-sensitivity or a diffusion of the spectral sensitizer into the adjacent layers, which will cause the spectral sensitization of the adjacent layers and deteriorate their color reproducibility to a great extent.

The principal object of the present invention is to provide a silver halide color photographic light-sensitive material with an excellent color reproducibility by incorporating certain dyestuffs therein to avoid the above-mentioned drawbacks.

SUMMARY OF THE INVENTION The above object of the present invention is attained by incorporating in the blue-sensitive emulsion layer of a silver halide color photographic light sensitive material bearing on a support a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer (irrespective of the layer arrangement), each layer containing one or more color coupler compounds, a compound having the following formula wherein R represents a sulfoalkyl group or a sulfoaralkyl group, and Z and Q respectively represent an atomic group necessary to complete a heterocyclic nucleus.

The alkyl of the sulfoalkyl group preferably has from 2 to 4 carbon atoms, and the sulfoalkyl group includes, e.g., a fi-sulfoethyl group, a 'y-sulfopropyl group, a 'ysulfobutyl group, and a a-sulfobutyl group. The sulfoaralkyl group includes e.g., a p-sulfobenzyl group and a psulfophenethyl group. The nucleus formed by Z includes, e.g., a benzothiazole nucleus, a benzoselenazole nucleus, a benzoxazole nucleus, a a-naphthothiazole nucleus, a anaphthoxazole nucleus and a fi-naphthoxazole nucleus, and the nucleus formed by Q includes, e.g., a rhodanine nucleus, a Z-thioxazoline-thione nucleus and a thiohydantoin nucleus.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 to 3 show the spectral sensitivity of various emulsion layers containing various dyestufls, including the dyestuif of the present invention.

3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The compound represented by the above general formula may be exemplified by the following compounds:

N ZL S the.

ling;

OCEIFL (CH2)3S or NH:

Dyestufl VII N O J: S

N *NH:

I C 2H5 (fHzS C\ NH! (O Hm S or i) Dyestufl VIII However, the present invention is not restricted to the above compounds exclusively.

The compound shown by the above general formula may be synthesized by any known process, as disclosed in US. Pat. 2,519,001.

The spectral sensitizer of the present invention can spectrally sensitize in the spectral sensitivity range of from 440 to 530 mp, and preferably is incorporated in an amount of from 0.01 to 0.5 g. per mole of silver halide. If the sensitizer is incorporated in an amount exceeding the above range, a decrease in spectral sensitivity occurs in the neighborhood of a wave length of about 430 mp. and, consequently, a corresponding decrease of the T618:- tive sensitivity to blue light occurs.

The coupler contained in the silver halide color photographic light-sensitive material of the present invention is not restricted and may be any conventional coupler compound.

The photographic light-sensitive material may also contain a stabilizer such as 5-methyl-7-hydroxy-1,3,5-triazaindolizine, a hardener such as a sodium salt of 2,4-dichloro- 6-hydroxyl-1,3,5-triazine, a coating aid such as dodecyl benzene sulfonate, a pH adjusting agent such as citric acid or sodium carbonate, a color-turbidity preventing agent such as vinylmethylimidazole homopolymer or copolymer, and other conventional additives.

Useful as the silver halide emulsion, there are a silver iodobromide emulsion, a silver bromide emulsion, and a silver chloroiodobromide emulsion.

As the binder, there may be used natural high molecular weight compounds, such as gelatin, casein or albumin, synthetic high molecular weight compounds, such as polyvinyl alcohol or polyvinyl pyrrolidone, and mixtures thereof.

The color photographic light-sensitive material of the present invention has the advantage that it gives a color image showing more vivid hue than prior color photographic light-sensitive materials. In addition, in prior silver halide color photographic lightsensitive materials in which the green-sensitive emulsion layer and the red-sensitive emulsion layer contain spectral sensitizers, but the blue-sensitive emulsion layer contains no spectral sensired-sensitive emulsion layers and, consequently, the loss of color balance among the three layers is small.

The present invention will now be further illustrated by the following detailed examples.

In the examples, there were used, for comparison purposes, known compounds having the following structural formulae:

H *E: HLNFOHCH- s (52H, ol f s =CH-CH S N Cl LS is N S H C f (CH2):4 2 .',)s

N S in on @3 0 ONHCuHzs Coupler 2 (magenta) 0 H25 C O N H1 Coupler 3 (yellow) Coupler 4 (yellow) CBHIT Q-c o CHzCONHQ-C ON\ Coupler 5 (yellow) COCQH Coupler 6 (yellow) 2 s O-NHCOCHflO-QNHCOCHOQ on t- O 5H1] Coupler 7 (yellow) (17 O O C 2H2s EXAMPLE 1 Preparation of the red-sensitive emulsion To a silver iodobromide emulsion prepared in accord-- ance with the process disclosed in Belgian Pat. 690,435 there was added a rnethanolic solution of anhydro-5,5'- dichloro-3',9-diethyl 3 (B-sulfobutyl)-selenacanbocyanine hydroxide in an amount of 0.2 millimole per mole of silver halide.

Separately 1 g. of N-n-dodecyl-1-hydroxy-4-chloro-2- naphthoic acid amide (coupler l), as a cyan coupler, was dissolved by heating in 2 ml. of dibutyl phthalate and the resulting solution was emulsified in 10 g. of a 10 wt. percent aqueous solution of gelatin using sodium dodecyl sulfate as a dispersant. The emulsion was added to the above sensitizer-containing silver halide emulsion in such a proportion as to provide 0.15 g. of the coupler per mole of silver halide. To the thllS-lfOIlIlCd emulsion was added a stabilizer, a hardener, a coating aid, a pH adjusting-agent and a color-turbidity preventing agent.

Preparation of the green-sensitive emulsion To a silver iodobrornide emulsion prepared in accordance with the process disclosed in Belgian Pat. 690,435, there was added 3,3',9'-triethyl 5,5 diphenyl-ox'acarbocyanine iodide in an amount of 0.2 millimole per mole of silver halide.

Separately, l g. of 1-phenyl-3-dodecylamino 5-pyrazolone (coupler 2), as a magenta coupler, was dissolved by heating in 2 ml. of tricresyl phosphate and the resulting solution was emulsified in 10 g. of a 10 wt. percent aqueous solution of gelatin using sodium dodecyl sulfate as a dispersant.

The thus-formed emulsion was added to the above sensitizer-containing silver halide emulsion in such a proportion as to provide 0.15 g. of the coupler per mole of silver halide. To the emulsion was added a stabilizer, a hardener, a coating aid, a pH adjusting agent and a color turbidity preventing agent.

Preparation of the blue-sensitive emulsion A silver iodobromide emulsion prepared in accordance with the process disclosed in Belgian P at. 690,435 was divided into three portions, and to two of them were added a rnethanolic soultion of dyestulf I of the present invention and a rnethanolic solution of comparison dyestulf (1) in amounts of 0.2 millimole per mole of silver halide, separately.

In addition, 1 g. of 4dodecylbenzoyl-2'-methoxy-acetanilide (coupler 3), as a yellow coupler, was dissolved by heating in 2.5 ml. of dibutyl phthalate and the resulting solution was emulsified in 10 g. of a 10 wt. percent aqueous solution of gelatin using sodium dodecyl sulfate as a dispersant.

To the above mentioned three portions of silver halide emulsion, two of which contain sensitizers while the other contains no sensitizer, there was added a coupler emulsion in such a proportion as to provide 0.22 g. of coupler per mole of silver halide. To each silver halide emulsion was then added a stabilizer, a hardener, a coating aid, a pH adjusting agent and a color-turbidity preventing agent.

Manufacture of silver halide color photographic light-sensitive material The three emulsions prepared above, were applied to a cellulose triacetate base having thereon an anti-halation layer. Namely, over the anti-halation layer on the base there was applied, in turn, the red-sensitive emulsion layer, a thin gelatin layer, the green-sensitive emulsion layer, the yellow filter layer containing colloidal silver, a bluesensitive emulsion layer and a protective gelatin layer successively. Thus, there was obtained a silver halide color photographic light-sensitive material containing no sensitizer in its blue-sensitive layer, a silver halide color photographic light-sensitive material containing dyestufi I in its blue-sensitive emulsion layer (in accordance with the present invention) and a silver halide color photographic light-sensitive material containing comparison dyestuif (l) in its blue-sensitive emulsion layer.

Exposure and processing The three color photographic light-sensitive materials each having the three basic emulsion layers as mentioned above were exposed by means of an ordinary spectrophotometer. Separately, the above three silver halide photographie light-sensitive materials, just after manufacture and after aging at 50 C., 70% RH. for 48 hours, were exposed by means of a sensitometer using an ordinary continuous wedge.

The color photographic light-sensitive materials thus exposed were developed using a developing solution of the following composition at 24 C. for minutes, washed with water, subjected to hardening, washed with water and subjected to the second reversal exposure.

COMPOSITION OF THE DEVELOPING SOLUTION N-methyl-p-aminophenol 4.5 Hydroquinone 4.5 Anhydrous sodium sulfite 50 Sodium carbonate monohydrate 30 Potassium bromide 1 Potassium thiocyanate 2 Water to make 1 liter.

The photographic light-sensitive materials were then subjected to color development at 24 C. for minutes using a color developing solution of the following composition and subsequently washed with Water, bleached, washed with water, fixed and washed with water to obtain color positive images.

Water to make -1 liter.

The spectrally sensitive ranges determined by a spectrophotometer are shown in FIG. 1 for the three emulsions described above.

In FIG. 1, curve 1 shows the spectral absorption for the blue-sensitive emulsion layer having no sensitizer incorporated therein, spectral absorption curve 2 is of a blue-sensitive emulsion layer having incorporated therein comparison dyestuif (1), and spectral absorption curve 3 is of a blue-sensitive emulsion layer having incorporated therein dyestutf I of the present invention. It is obvious from FIG. 1 that the spectral sensitivity range of the sensitive material having a dyestuif incorporated therein is extended toward the longer wave length side in com- 8 parison with that of an unsensitized photographic lightsensitive material. However, the spectral sensitivity of the blue-sensitive emulsion containing comparison dyestutf (l) is so extended up to 560 mp. as to exhibit a color sensitivity to green light, and, therefore, dyestufl (1) is inadequate for use as a sensitizer for the bluesensitive emulsion layer. In contrast thereto, the bluesensitive emulsion layer containing the sensitizing dyestufi I of the present invention has a low sensitivity in the longer wave length side and little color sensitivity in the region of wave lengths greater than 530 my and, therefore, dyestuff I is desirable as a sensitizing dyestufi for the blue-sensitive emulsion layer.

The optical densities of the processed blue-sensitive emulsion layers were measured and the relative sensitivities were determined in terms of the relative quantity of exposure requisite for obtaining a density of 1.0, assuming that the relative sensitivity of a blue-sensitive emulsion layer containing no sensitizer, and just after coating, is 100. The results are shown in Table 1. In Table 1, the D min. values are the measured values of optical density to blue light in the highlight portion which indicates the degree of residual stain due to the dyestuff and other impurities added thereto.

TABLE 1 After aging under high tem rature Just alter coating and humidity condltidii Relative Relative sensitivity D min. sensitivity D min;

None 0. 06 95 0. 07 Dye (1) 150 0. 07 0. O8 Dye I 0. 07 138 0. 08

dyestufi (1) decreased to 120, while that of the bluesensitive emulsion layer containing dyestufi I of the present invention was still as high as 138. This indicates that a blue-sensitive emulsion layer loses some sensitivity during storage under high temperature and humidity conditions and also that the sensitizer of the present invention is evidently superior to the known sensitizer. In addition, the sensitizer of the present invention gave too little stain to cause trouble.

EXAMPLE 2 The same procedure as in Example 1 was repeated except that comparison dyestufls (2) and (3) and dyestufi II of the present invention were used, separately, in place of the sensitizers of Example 1 in the blue-sensitive emulsion layers.

The results of the spectrophotometry are shown in FIG. 2, and the results of the sensitometry are in Table 2. As is evident from Table 2, sensitizing dyestufi II of the present invention has a high relative sensitivity after storage under high temperature and humidity conditions, and, in fact, as well as the sensitivity just after coating and also, it is superior to the comparison dyestuffs (2) and (3). In addition, the D min. value in the highlight portion is too low to cause any trouble.

In FIG. 2, curve 1 is a spectral absorption curve of the blue-sensitive emulsion layer, containing no sensitizer, Curve 2 is a spectral absorption curve of blue-sensitive emulsion layer containing comparison dyestufi (2), curve 3 is a spectral absorption curve of the blue-sensitive emulsion layer containing comparison dyestuff (3) and curve 4 is a spectral absorption curve of the blue-sensitive emulsion layer containing dyestutf H.

9 As is evident from FIG. 2, dyestufi II of the present invention is shown to have a desirable spectral sensitivity for use as a sensitizer for blue-sensitive emulsion layers.

TABLE 2 After agilng under high temperature The same procedure as in Example 1 was repeated except that the sensitizer for the blue-sensitive emulsion layer was replaced by one of the above dyestufis IV, V, VI, VII and VIII and the above comparison dyestufi (4).

The results of sensitometry and of spectrophotometry are shown in Table 3 and FIG. 3, respectively.

TABLE 3 After storage under high temperature and humidity con- Just after coating ditions Relative D Relative Dyestufi sensitivity min. sensitivity D min.

None 100 0.00 97 0. 07 IV 160 0. 07 130 0.08 V 155 0.07 145 0.08 VI 135 0. 130 0. 09 VII 133 0.07 130 0.09 vrrr 140 0. 0a 135 0.00 Comparison dyestufi (4).-- 95 0. 14 92 0. 18

In the accompanying drawings, FIG. 3 indicates a spectral absorption curve 1 of the blue-sensitive emulsion layer containing no sensitizer, a spectral absorption curve 2 of the blue-sensitive emulsion layer containing comparison dyestuif (4), a spectral absorption curve 3 of the bluesensitive emulsion layer containing one of the dyestufi's IV and V, and a spectral absorption curve 4 of the bluesensitive emulsion layer containing one of the dyestuffs VI, VII and VIII.

The blue-sensitive emulsion layer containing comparison dyestufi (4) was little improved in color sensitivity and had a yellow residual stain, while the blue-sensitive emulsion layer containing on of the dyestuffs of the present invention had a desirable spectral sensitivity distribution and little residual stain and retained a high relative sensitivity even after storage under high temperature and humidity conditions.

Although the photographic emulsions are coated on cellulose acetate film in the examples of this invention, it is to be understood that the photographic silver halide emulsions may be advantageously coated on any conventional support materials for photographic light-sensitive materials, including glass, paper, polyolefin coated paper, cellulose acetate, cellulose nitrate and synthetic film-forming resinous materials, such as the polystyrenes, the polyesters, or the polyamides.

What is claimed is:

1. A color photographic light-sensitive material comprising a support having coated thereon a red-sensitive silver halid emulsion layer containing a cyan-color forming coupler, a green-sensitive silver halide emulsion layer containing a magenta-color forming coupler, and a bluesensitive silver halide emulsion layer containing a yellow forming coupler and a compound represented by the formula wherein R is a member Selected from the group consisting of a sulfoalkyl group and a sulfoaralkyl group, 2 is a member selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a benzoxazole nucleus,

an a-naphthothiazole nucleus, an u-naphthoxazole nucleus, a fi-naphthoxazole nucleus, and further, wherein Q is a member selected from the group consisting of a rhodanine nucleus, a 2-thioxazolinethione nucleus, and a thiohydantoin nucleus.

2. The color photographic light-sensitive material as in claim 1, wherein the amount of said compound is from 0.01 to 0.5 gram per one mole of silver halide.

3. The color photographic light-sensitive material as in claim 1, wherein R is a member selected from the group consisting of a fl-sulfoethyl group, a -sulfopropyl group, a 'y-sulfobutyl group, a fi-sulfobutyl group, a p-sulfobenzyl group and a p-sulfophenethyl group.

4. The color photographic light-sensitive material as in claim 1, wherein said compound is (l Hz) aS Os'H 2116)! 5. The color photographic light-sensitive material as in claim 1, wherein said compound is Nag t,

( aHs 1 2) a a' a 7) a 6. The color photographic light-sensitive material as in claim 1, wherein said compound is 7. The color photographic light-sensitive material as in claim 1, wherein said compound is 8. The color photographic light-sensitive material as in claim 1, wherein said compound is 1 1 9. The color photographic light-sensitive material as in claim 1 wherein said compound is 10. The color photographic light-sensitive material as in claim 1 wherein said compound is 5,3. CHrSC I NH: H2): 8 OFQQ 11. The color photographic light-sensitive material as in claim 1 wherein said compound is 12. A color photographic light-sensitive material comprising a support having coated thereon, a red-sensitive silver halide emulsion layer containing a cyan-color forming coupler, a green-sensitive silver halide emulsion layer containing a magenta-color forming coupler, and a bluesensitive silver halide emulsion layer containing a yellow forming coupler, and a compound represented by the formula R-I-'I--o=0'o=0 wherein R is a member selected from the group consisting of a sulfoalkyl group and a sulfoaralkyl group; Z is a member selected from the group consisting of a benzothiozole nucleus, a 'benzoselenazole nucleus, a benzoxazole nucleus, an a-naphthothiazole nucleus, an a-naphthoxazole nucleus, and a fi-naphthoxazole nucleus; and Q is a References Cited UNITED STATES PATENTS 2,161,331 6/1939 Brooker et al 96-102 2,493,748 1/1950 Brooker et al 96-102 2,519,001 8/1950 Spraque 961-02 3,384,486 5/1968 Taber et al. 96-74 3,480,434 11/1969 Hanna -0 96-74 3,522,052 7/1970 Shi'ba et al. 96-100 ROBERT F. BURNETT, Primary Examiner G. W. MOXON II, Assistant Examiner US. Cl. X.R. 96-100, 139, 

